Cupriferous disazo-dyestuffs



2,929,673 Patented Mar. 22, 1960 nited States Patent ice present process can be made, for example, by coupling 2,929,673 a tetrazotized 3:3'-dialkoxy-4:4-diaminodiphenyl, es-

pecially dianisidine, in either order of succession, on one CUPRIFEROUS DISAZO'DYESTUFFS side, with a Z-phenylamincor Z-benzoylamino-S-hydrox- Hans Luzi Sclmcan, Bettingen, Switzerland, assignmto 5 ynaphthalene-7-sulfonic acid which is free from further Ciba Limited, Basel, Switzerland,aSwiss firm groups imparting solubility in water and may contain further substituents in the benzene radical and, on the No g ig gg ggf z61956 other side, with Z-hydroxy-naphthalene-:8-disulfonic n acid. The amino group of the 2-arnino-5-hydroxynaph- Claims priority, application Switzerland 10 thalene-7-sulfonic acid may either be an unsubstituted February 10, 1955 phenylaminoor benzoylamino-group or, for example, a 7 methylphenylamino, para-methoxyphenylamino, paral0 Clams (CL 8-26) chlorophenylamino or chlorobenzoylamino group.

Especially valuable dyestuffs of this invention are ob- This invention provides cupriferous disazo-dyestuffs tained by using a starting material of the formula a no I I no car H035 NH(G 0)'. -1R

which, in the form of free acids, correspond to the forin which R represents a benzene radical free from groups mula: imparting solubility in water, and n represents the whole number 1 or 2. (I) The following are a few examples of derivatives of 2- amino-S-hydroxynaphtbalene-7-sulfonic acid, which can I I I l be used in the manner described above with the other components to give starting materials which yield valusofl H035 x able dyestuffs as the result of the coppering treatment:

Hots

2-phenylamino-S-hydroxynaphthalene-7-sulfonic acid, 2 (Para methylphenylamino) 5 hydroxynaphthalene- 7-sulfonic acid,

2 (para chlorophenylamino) 5 hydroxynaphthalene- 7-sulfonic acid, 2 (para methoxyphenylamino) 5 hydroxynaphthalene-7-sulfonic acid, 2-benzoylamino-5-hydroxynaphthalene-7-sulfonic acid,

2 (para chlorobenzoylamino) 5 hydroxynaphthalene-7-sulfonic acid, 2. (2':4 dichlorobenzoylamino) 5 hydroxynaphthalene-7-sulfonic acid.

The treatment of the disazo-dyestufis of the Formulae 2 and 3 with an agent yielding copper is carried out under metric proportion of copper and the correct position of conditions such that the formation Of the OIthOIOITh O the copper atoms in the complex, but the distribution of Y Y- PP P accompanied y p fi g the main and secondary valences in the complex union of so p f the q y g p especlally methoxy groups, p the copper is not up to the present known with certainty. 611i 9 i116 p p yl P P Methods or The invention also provides a process for the manuy g o t fl ps dealkylatlng coppermg treatment are facture of the above cupriferous disazo-dyestulfs, whereknown. Espq advantageous 111 y 08565 18 t in a disazo-dyestufi which, in the form of the free acid, process In whlqh the qppe earned out f r one or corresponds to the general formula several hours in the viclmty of 100 C. in an aqueous medium with the use of a copper tetrammine complex O A1ky1 OH and in the presence or absence of an excess of ammonia. In some cases it is especially advantageous to use the I l l L process of Patent No. 2,536,957, granted January 2, 1951, 50 to Henri Riat et al., in which the process is carried out in which X represents an NH(C o)rtn group, R standing for a monocyclic aromatic radical and n for a l or 2, viz. X represents a phenylamino or benzoylamino group which may contain substituents, and which dyestulfs contain as the sole groups imparting solubility in water the sulfonic acid groups shown in the 45 formula.

This formula undoubtedly indicates the correct stoichio- (2) H O Allryl-O 503E Hoas in the presence of an hydroxyalkylamine, especially eth anolamine, or a copper complex derived therefrom.

Complex copper compounds, which are obtained from disazo-dyestufis of the formula in which X has the meaning given above, and which dyestufi contains as the sole groups imparting solubility M- in water the three sulfonic acid groups shown in the formula, is treated with an agent yielding copper under conditions such that the formation of the ortho:ortho'- HO:S

t|3-AJkyl Ho dihydroxy-azo-copper complex is accompanied by split- :8 X

ting up of the -0-A1kyl groups. 0

The disazo-dyestufis used as starting materials 1n the g in which R represents a mononuclear carbocyclic I I p, v aromatic radical free from groups imparting waterand which dyestuff contains in admixture a cupriferous solubility, and n represents a whole number or at the disazo dyestufi which in its free acid state corresponds most 2. to the formula OCu-0 I I [I I 2. A cupriferous disazo dyestuff which in its free acid I State corresponds to the formula m which -formulae R represents a mononuclear carhocyclic aromatic radical'tree from'gfoups imparting'water- I I I I solubility; andn represents a whole number of at the most 2, the quantity of the dyestuffs I and II considered together being such that the mixture contains at least H033 of dyestufl I and at most 60% ofdyestufi II. HO 8 5 A cupriferous disazo dyestufl which in its free acid 5 state corresponds to the formula in which R represents a mononuclear carbocychc aromatic radical free from groups imparting waterand which dyestufi contains in admixture'a cupriferous solubility. disazo dyestufi which in its free acid state corresponds to the formula Boss 0-Cu0 0--Cu-0 I l l H038 NHC 0-R 3.. A cupriferous disazo dyestufi which in its free acid in which formulae R represents a mononuclear carbostate corresponds to the formul'a I cyclic aromatic radical free from groups imparting water- Cu 0 0Cu0 in which R represents a mononuclear carbocyclic aromatic radical free from groups imparting watersolubility; the quantity of the dyestufis I and H consolubility. sidered together being such that the mixture contains at 4. A cupriferous disazo dyestufi which in its free acid least 40% of dyestufi I and at most of dyestufi II.

state corresponds to the formula Hons I n I I I l iarors-I V Hols 2:922:91? 7 8 6, The cupriferous disazo dycstutf which in its free 7 acid state corresponds to the formula son: 7 Ems 1101s 7 I 7. The cupriferous disazo dyestufi which in its free acid state corresponds to the formula 8. The cupriferous disazo dyestujfi which in its free acid state corresponds to the formula 9. A cupriferous disazo dyestufi which in its free acid state corresponds to the formula V Hots of which dyestufi from 40% to 100% contain the sulfonic acid group in 8-position and at most 60% contain the so sulfonic acid group in 3-position of the terminal naphthalene nucleus.

A up l xeus d s s dyqstufi which n t fr acid state corresponds to the formula H I l I v Lnors Ihfim cs Cite in the 1': this P en STATES PATENTS 1',889;732'- Stusser et al Nov. 29, 19312; 2,668,167 Monnier Feb. 2, 1954 2,714,588 Keller Aug. 2, 1955 2,817,656 Bissell 1 957 i ii $1 1 1 T NTTED STATES PATENT oTiucE CERTIFICATE 9F CORRECTION Fatent No. 2,92%673 March 22 1960 Hans Luzi Schucan It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, line 42, after for: strike out "a"; column "Z claims 9 and 10 the lefthand portion of the formulas, each occurrence should appear as shown below instead of as in the patent:

Lao s Signed and sealed this 30th day of August 1960 (SEAL) Attest:

ERNEST W, SWIDER ROBERT C. WATSON Attesting Officer Commissioner of Patents 

1. A CUPRIFEROUS DISAZO DYESTUFF WHICH IN ITS FREE ACID STATE CORRESPONDS TO THE FORMULA
 9. A CUPRIFEROUS DISAZO DYESTUFF WHICH IN ITS FREE ACID STATE CORRESPONDS TO THE FORMULA 